1,3-Benzodioxol-5-ol (Sesamol) by Asch

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Bioactivities (288)

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Reactions (33)

Substances (1)

Targets (14)

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Citations (50)

References

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Rx-ID: 123313 Find similar reactions

95%

Stage #1: With 3-chloro-benzenecarboperoxoic acid

Dakin oxidation; 0.0833333 h; Stage #2: With sodium hydroxide

0.0833333 h; Further stages.;

Da Silva, Emerson Teixeira; Camara, Celso Amorim; Antunes; Barreiro, Eliezer J.; Fraga, Carlos A. M.

Synthetic Communications, 2008 , vol. 38, # 5 p. 784 - 788 Title/Abstract Full Text View citing articles Show Details

89%

With sulfuric acid; dihydrogen peroxide; boric acid in tetrahydrofuran; water

T=20°C; Oxidation; 3.5 h;

Roy, Amrita; Reddy; Mohanta, Pramod K.; Ila; Junjappa

Synthetic Communications, 1999 , vol. 29, # 21 p. 3781 - 3791 Title/Abstract Full Text View citing articles Show Details

78%

With sulfuric acid; dihydrogen peroxide; boric acid; 3-butyl-1methyl-1H-imidazol-3-ium hexafluorophosphate

T=0°C; Dakin reaction;

Zambrano, Jorge L.; Dortab, Romano

Synlett, 2003 , # 10 p. 1545 - 1546 Title/Abstract Full Text View citing articles Show Details

77%

Stage #1: With formic acid; dihydrogen peroxide in dichloromethane; water

Bezerra-Netto, Heleno J.C.; Lacerda, Daniel I.; Miranda, Ana Luisa P.; Alves, Helio M.; Barreiro, Eliezer J.; Fraga, Carlos A.M.

18 h; Heating; Stage #2: With sodium hydroxide in dichloromethane; water

T=20°C; 0.25 h;

Bioorganic and Medicinal Chemistry, 2006 , vol. 14, # 23 p. 7924 - 7935 Title/Abstract Full Text View citing articles Show Details

56%

With Oxone; EDTA; sodium hydrogencarbonate in water; acetonitrile

Oxidation; 1 h;

Webb, Kevin S.; Ruszkay, Stephen J.

Tetrahedron, 1998 , vol. 54, # 3-4 p. 401 - 410 Title/Abstract Full Text View citing articles Show Details

35%

With formic acid; dihydrogen peroxide

T=5°C; 16 h;

Devakumar, C.; Saxena, V. S.; Mukerjee, S. K.

Agricultural and Biological Chemistry, 1985 , vol. 49, # 3 p. 725 - 730 Title/Abstract Full Text Show Details

With peracetic acid; toluene-4-sulfonic acid; acetic acid

Erwaermen des Reaktionsgemisches mit aethanol. Kalilauge;

Boeeseken et al.

Recueil des Travaux Chimiques des Pays-Bas, 1936 , vol. 55, p. 815,817 Full Text View citing articles Show Details

Beroza

Journal of Agricultural and Food Chemistry, 1956 , vol. 4, p. 49,51, 52 Full Text View citing articles Show Details

Wilkinson

Biochemical Journal, 1956 , vol. 63, p. 601,603 Full Text View citing articles Show Details

With sulfuric acid; dihydrogen peroxide in methanol

T=20°C; 48 h;

Nam, Nguyen-Hai; Kim, Yong; You, Young-Jae; Hong, Dong-Ho; Kim, Hwan-Mook; Ahn, Byung-Zun

Bioorganic and medicinal chemistry letters, 2002 , vol. 12, # 17 p. 2345 - 2348 Title/Abstract Full Text View citing articles Show Details

Stage #1: With 3-chloro-benzenecarboperoxoic acid

Baeyer-Villiger oxidation; Stage #2: With sodium hydroxide

Sa E Sant'Anna; Evangelista; Alves; Raslan

Chemistry of Natural Compounds, 2005 , vol. 41, # 4 p. 385 - 387 Title/Abstract Full Text View citing articles Show Details

Multi-step reaction with 2 steps 1: 900 mg / m-chlorperbenzoic acid / CH2Cl2 / 2.5 h 2: methanolic KOH / methanol; tetrahydrofuran / 30 h / 10 °C View Scheme

Rohatgi, B. K.; Khanna, R. N.

Indian Journal of Chemistry, Section B: Organic Chemistry Including Medicinal Chemistry, 1983 , vol. 22, # 11 p. 1150 Title/Abstract Full Text Show Details

Multi-step reaction with 2 steps 1: 3-chloro-benzenecarboperoxoic acid / dichloromethane / 1 h / 0 20 °C 2: potassium hydoxide / methanol; water / 0.03 h / 20 °C View Scheme

Gangar, Mukesh; Chouhan, Mangilal; Goyal, Sandeep; Harikrishnan; Chandran; Ittuveetil, Avinash; Nair, Vipin A.

Tetrahedron Letters, 2016 , vol. 57, # 52 p. 5931 - 5934 Title/Abstract Full Text View citing articles Show Details

With dihydrogen peroxide; sodium hydroxide in methanol; water

T=45 - 60°C; 2 h; Reagent/catalyst; Hide Experimental Procedure

UBE INDUSTRIES LIMITED; KIMURA, KEISUKE; OOMORI, KIYOSHI; KAIDA, SUZUE; NISHIMURA, KOSUKE

Patent: JP2017/101020 A, 2017 ; Location in patent: Paragraph 0159-0161 ;

28.5 g

Title/Abstract Full Text Show Details

1.2:Synthesis of 3,4-methylenedioxyphenol

Mechanical stirrer,To a 2 L separable flask equipped with a condenser and equipped with a jacket was added methanol6.2 g of 98percent by weight sulfuric acid and 92.0 g of the initial retention of heliotropin produced in step 1 (GC purity of heliotropin 96.5 areapercent) were mixed and the temperature of the solution was raised to 45 ° C. It warmed up. Thereafter, 54.1 g of 60 wtpercent hydrogen peroxide water was added dropwise. The temperature of the solution was kept at 60 ° C., and aging was carried out for 1 hour from the end of the hydrogen peroxide dropwise addition. After ripening for 1 hour, 49.0 g of a 20 wtpercent sodium hydroxide aqueous solution containing 16.8 g of sodium 3,4-methylenedioxyphenoxide (sodium salt of sesamol) was added dropwise at a solution temperature of 60 ° C., and the solution was neutral Respectively. Thereafter, 37.2 g of a 20percent by weight sodium hydroxide aqueous solution was added dropwise and aged at 60 ° C. for 1 hour. The concentration of hydrogen peroxide after aging was 516 ppm, and the pH was 8.2. To the obtained solution, 9.2 g of 30percent by weight HCl was added and the temperature of the solution was cooled from 60 ° C. to 25 ° C. to precipitate an inorganic salt and a high-boiling component, followed by filtration under reduced pressure. As a result, 872.5 g of filtrate (including 73.9 g of sesamol, reactionThe reaction yield to heliotropin contained in the initial distillate used at times was 74.1percent) and 28.5 g of filtered matter was obtained.

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16 g

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Rx-ID: 1718747 Find similar reactions

With water; potassium hydoxide in methanol

T=50°C; 1 h;

Singh, Pragya; Faridi, Uzma; Srivastava, Suchita; Kumar, Jonnala Kotesh; Darokar, Mahender Pandurang; Luqman, Suaib; Shanker, Karuna; Chanotiya, Chandan Singh; Gupta, Atul; Gupta, Madan Mohan; Negi, Arvind Singh

Chemical and Pharmaceutical Bulletin, 2010 , vol. 58, # 2 p. 242 - 246 Title/Abstract Full Text View citing articles Show Details

With potassium hydroxide in tetrahydrofuran; methanol

T=10°C; 30 h; Yield given;

Rohatgi, B. K.; Khanna, R. N.

Indian Journal of Chemistry, Section B: Organic Chemistry Including Medicinal Chemistry, 1983 , vol. 22, # 11 p. 1150 Title/Abstract Full Text Show Details

With potassium hydroxide in methanol

1 h; Ambient temperature; Yield given;

Syper, Ludwik

Synthesis, 1989 , # 3 p. 167 - 172 Title/Abstract Full Text Show Details

With potassium hydroxide in methanol

2.5 h; Ambient temperature; Yield given;

Saito, Naoki; Tashiro, Kyoichi; Maru, Yukie; Yamaguchi, Kentaro; Kubo, Akinori

Journal of the Chemical Society, Perkin Transactions 1: Organic and Bio-Organic Chemistry (1972-1999), 1997 , # 1 p. 53 - 70 Title/Abstract Full Text Show Details

With potassium hydroxide in methanol; water

Chandrasekhar; Reddy, N. Ramakrishna; Rao, Y. Srinivasa

Tetrahedron, 2006 , vol. 62, # 51 p. 12098 - 12107 Title/Abstract Full Text View citing articles Show Details

With methanol; potassium hydroxide

T=20°C;

Duan, Xin-Fang; Zeng, Jing; Zhang, Zhan-Bin; Zi, Guo-Fu

Journal of Organic Chemistry, 2007 , vol. 72, # 26 p. 10283 - 10286 Title/Abstract Full Text View citing articles Show Details

With potassium hydoxide in methanol; water

T=20°C; 0.0333333 h; Hide Experimental Procedure

Gangar, Mukesh; Chouhan, Mangilal; Goyal, Sandeep; Harikrishnan; Chandran; Ittuveetil, Avinash; Nair, Vipin A.

Tetrahedron Letters, 2016 , vol. 57, # 52 p. 5931 - 5934 Title/Abstract Full Text View citing articles Show Details

Synthesis of Benzo[d][1,3]dioxol-5-ol (8)

To the stirred solution of benzo[d][1,3]dioxole-5-carbaldehyde 7 (1 g, 6.7 mmol, 1.0 equiv) in DCM was added mCPBA (1.72 g, 10.1 mmol, 1.5 equiv) and stirred for another hour at rt. After the full conversion of starting material (monitored by the TLC) the reaction mixture was extracted with DCM. It was dried over anhydrous sodium sulfate and the solvent was evaporated under the reduced pressure to give the crude product. The crude product was taken in MeOH and aq. KOH was added to the reaction mixture and stirred at rt. After the completion of the reaction, MeOH was evaporated under reduced pressure. The pH was adjusted to 4-5 by the addition of conc. HCl and the reaction mixture was extracted with ethyl acetate. It was dried over anhydrous sodium sulfate and the solvent was evaporated under the reduced pressure to give the crude product. The crude product was purified by column chromatography over silica gel (60-120 mesh) using petroleum ether/EtOAc (90:10) as the eluent to afford desired product.

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Rx-ID: 33647868 Find similar reactions

88%

With copper acetylacetonate; N,N′-bis(4-hydroxyl-2,6dimethylphenyl)oxalamide; water in water; dimethyl sulfoxide

T=130°C; 24 h; Schlenk techniqueInert atmosphere;

Xia, Shanghua; Gan, Lu; Wang, Kailiang; Li, Zheng; Ma, Dawei

Journal of the American Chemical Society, 2016 , vol. 138, # 41 p. 13493 - 13496 Title/Abstract Full Text View citing articles Show Details

51%

With Herrmann catalyst; C29H45Pt; caesium carbonate in water; N,N-dimethyl-formamide

T=130°C; 0.5 h; Inert atmosphereMicrowave irradiation;

Yu, Chao-Wu; Chen, Grace S.; Huang, Chen-Wei; Chern, Ji-Wang

Organic Letters, 2012 , vol. 14, # 14 p. 3688 - 3691 Title/Abstract Full Text View citing articles Show Details

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Synthesize Find similar Rx-ID: 42209585 Find similar reactions

A: 20 %Chromat. B: 24 %Chromat. C: 30 %Chromat.

in cyclohexane

T=25°C; Inert atmosphereIrradiation; Wavelength; Hide Experimental Procedure

Iguchi, Daniela; Erra-Balsells, Rosa; Bonesi, Sergio M.

Tetrahedron, 2016 , vol. 72, # 16 p. 1903 - 1910 Title/Abstract Full Text View citing articles Show Details

General procedure: General procedure for aryl 3-methyl-2-butenoate esters. Solutions of esters (1–9; 0.106mmol) were prepared in different organic media (100mL). Photoirradiations of the esters were performed as follow: i) analytical scale: a 2mL aliquot of solution was placed in a stoppered 3mL quartz cell and degassed with argon for 20min; ii) preparative scale: a 65mL aliquot was placed in a stoppered 100mL Erlenmeyer quartz flask and degassed with argon for 30min. The quartz cell as well as the Erlenmeyer quartz flask were placed in a home made optical bench provided with the possibility to use two or four lamps. The solutions of the esters were stirred during the irradiation process. Irradiations with λexc=313nm were carried out with four phosphorous–coated lamps (HelioQuartz, each of 18 Watts) that give a nearly parallel beam at 313nm. Irradiations with λexc=254nm were carried with four germicide lamps (Philips, each of 20 Watts).

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With copper acetylacetonate; N,N′-bis(4-hydroxyl-2,6dimethylphenyl)oxalamide; potassium hydoxide in water; dimethyl sulfoxide

T=60°C; 24 h; Schlenk techniqueInert atmosphere;

Rx-ID: 43723355 Find similar reactions

Xia, Shanghua; Gan, Lu; Wang, Kailiang; Li, Zheng; Ma, Dawei

Journal of the American Chemical Society, 2016 , vol. 138, # 41 p. 13493 - 13496 Title/Abstract Full Text View citing articles Show Details

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With copper acetylacetonate; N,N′-bis(4-hydroxyl-2,6dimethylphenyl)oxalamide; water in water; dimethyl sulfoxide

T=80°C; 24 h; Schlenk techniqueInert atmosphere;

Rx-ID: 43723513 Find similar reactions

Xia, Shanghua; Gan, Lu; Wang, Kailiang; Li, Zheng; Ma, Dawei

Journal of the American Chemical Society, 2016 , vol. 138, # 41 p. 13493 - 13496 Title/Abstract Full Text View citing articles Show Details

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Multi-step reaction with 3 steps 1.1: 1,8-diazabicyclo[5.4.0]undec-7-ene / N,N-dimethyl-formamide / 0.5 h / 20 °C 1.2: 4 h / 0 °C / |Reflux 2.1: 3-chloro-benzenecarboperoxoic acid / dichloromethane / 1 h / 0 - 20 °C 3.1: potassium hydoxide / methanol; water / 0.03 h / 20 °C View Scheme

Rx-ID: 44079718 Find similar reactions

Gangar, Mukesh; Chouhan, Mangilal; Goyal, Sandeep; Harikrishnan; Chandran; Ittuveetil, Avinash; Nair, Vipin A.

Tetrahedron Letters, 2016 , vol. 57, # 52 p. 5931 - 5934 Title/Abstract Full Text View citing articles Show Details

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Rx-ID: 29512006 Find similar reactions

95%

With water; potassium hydroxide in methanol

T=50°C; 2 h;

Chemical and Pharmaceutical Bulletin, 2010 , vol. 58, # 2 p. 242 - 246 Title/Abstract Full Text View citing articles Show Details

95%

With water

T=20°C; 1.25 h; Hide Experimental Procedure

Khazaei, Ardeshir; Saednia, Shahnaz; Roshani, Liela; Kazem-Rostami, Masoud; Zare, Abdolkarim

Letters in Organic Chemistry, 2014 , vol. 11, # 3 p. 159 - 167 Title/Abstract Full Text View citing articles Show Details

General Procedure for Deacetylation of Esters Using PBNS in H2O

General procedure: A mixture of ester (1 mmol) and PBNS (30 mg) in H2O(2 mL) was stirred at ambient temperature. After completion of the reaction as monitored by TLC, the insoluble catalyst was separated by filtration. Water was removed by rotary evaporation and the residue was extracted with ethyl acetate(310 mL). The organic layer was dried over anhydrous Na2SO4. After evaporation of the solvent, the products were purified by column chromatography. The product’s purity was checked by TLC, it showed single spot of the final product, and evaporation of the solvent gave the desired pure products in good yields.

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Rx-ID: 37467513 Find similar reactions

He, Zhi; Jamison, Timothy F.

Angewandte Chemie - International Edition, 2014 , vol. 53, # 13 p. 3353 - 3357 Angew. Chem., 2014 , vol. 126, # 13 p. 3421 - 3425,5 Title/Abstract Full Text View citing articles Show Details

With air in tetrahydrofuran

T=-25°C; P=12929 Torr; 0.0566667 h; Green chemistry;

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Rx-ID: 34317777 Find similar reactions

A: 53% B: 17%

With potassium hydroxide in ethylene glycol

Reflux; Mechanism;

Chang, Junbiao; Wang, Shuyang; Shen, Zhenhua; Huang, Gang; Zhang, Yueteng; Zhao, Jing; Li, Changwei; Fan, Fangfang; Song, Chuanjun

Tetrahedron Letters, 2012 , vol. 53, # 50 p. 6755 - 6757,3 Title/Abstract Full Text Show Details

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Synthesize Find similar Rx-ID: 25607727 Find similar reactions

With alkaline phosphatase

pH=7.4; Aqueous phosphate bufferEnzymatic reaction; Hide Experimental Procedure

AMOREPACIFIC CORPORATION

Patent: WO2006/132479 A1, 2006 ; Location in patent: Page/Page column 15; Fig. 1 ; Title/Abstract Full Text Show Details

In order to examine whether the sesamol, 3-aminopropane phosphoric acid diester is hydrolyzed by phosphatase present on the skin into sesamol and 3-aminopropane phosphoric acid, the following test was performed. The sesamol, 3-aminopropane phosphoric acid diester of Example 1 and phsophatase were added in phosphate buffer (pH 7.4), followed by hydrolysis. As the phosphatase, alkaline phosphatase commercially available from Sigma- Aldrich Co. was used. The amount of 3-aminopropane phosphoric acid formed as the hydrolysis progressed was measured by HPLC (high- performance liquid chromatography), and the measurement results are shown in FIG. 1.As can be seen in FIG. 1, it was found that the sesamol, 3- aminopropane phosphoric acid diester can be hydrolyzed by phosphatase present on the skin into sesamol and 3-aminopropane phosphoric acid, so that it can simultaneously the activities of sesamol and 3-aminopropane phosphoric acid. With water; alkaline phosphatase

pH=7.4; Aqueous phosphate buffer; Product distribution / selectivity; Hide Experimental Procedure

AMOREPACIFIC CORPORATION

Patent: US2009/131686 A1, 2009 ; Location in patent: Page/Page column 5 ; Title/Abstract Full Text Show Details

EXPERIMENTAL EXAMPLE 3; In order to examine whether the sesamol, 3-aminopropane phosphoric acid diester is hydrolyzed by phosphatase present on the skin into sesamol and 3-aminopropane phosphoric acid, the following test was performed. The sesamol, 3-aminopropane phosphoric acid diester of Example 1 and phsophatase were added in phosphate buffer (pH 7.4), followed by hydrolysis. As the phosphatase, alkaline phosphatase commercially available from Sigma-Aldrich Co. was used. The amount of 3-aminopropane phosphoric acid formed as the hydrolysis progressed was measured by HPLC (high-performance liquid chromatography), and the measurement results are shown in FIG. 1.As can be seen in FIG. 1, it was found that the sesamol, 3-aminopropane phosphoric acid diester can be hydrolyzed by phosphatase present on the skin into sesamol and 3-aminopropane phosphoric acid, so that it can simultaneously the activities of sesamol and 3-aminopropane phosphoric acid.

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With hypophosphorous ether in water; acetonitrile

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Rx-ID: 28774743 Find similar reactions

Dichiarante, Valentina; Fagnoni, Maurizio; Albini, Angelo

%Chromat.

15 h; IrradiationInert atmosphere;

Green Chemistry, 2009 , vol. 11, # 7 p. 942 - 945 Title/Abstract Full Text View citing articles Show Details

Synthesize Find similar Multi-step reaction with 2 steps 1: m-chloroperoxybenzoic acid / CH2Cl2 / 18 h / Heating 2: potassium hydroxide / methanol; H2O View Scheme

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Rx-ID: 12139231 Find similar reactions

Chandrasekhar; Reddy, N. Ramakrishna; Rao, Y. Srinivasa

Tetrahedron, 2006 , vol. 62, # 51 p. 12098 - 12107 Title/Abstract Full Text View citing articles Show Details

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With titanium(III) chloride in acetonitrile

T=20°C; 24 h;

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Rx-ID: 9780725 Find similar reactions

Semwal, Abha; Nayak, Sandip K.

Synthesis, 2005 , # 1 art. no. Z16603SS, p. 71 - 74 Title/Abstract Full Text View citing articles Show Details

Synthesize Find similar With formic acid; dihydrogen peroxide

anschliessend Behandeln mit methanol. Kalilauge;

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Rx-ID: 166782 Find similar reactions

Sugawara

Nippon Nogei Kagaku Kaishi, 1959 , vol. 33, p. 648,650 Chem. Zentralbl., 1963 , vol. 134, p. 20767 Full Text View citing articles Show Details

Stage #1: With acetic anhydride; toluene-4-sulfonic acid in dichloromethane

T=40°C; Stage #2: With dihydrogen peroxide in dichloromethane; water

Heating / reflux; Stage #3: With hydrogenchloride in dichloromethane; water

pH=1; Hide Experimental Procedure

ENDURA S.P.A.

Patent: WO2004/92106 A2, 2004 ; Location in patent: Page 13 ; Title/Abstract Full Text Show Details

11:EXAMPLE 11. Synthesis of 3,4-methylenedioxo-phenol

A mixture of 17. 7G (100 MMOL) of 1- (1, 3BENZODIOXOL-5-YL)-1-PROPANONE, 26 ML of dichloromethane, 22.5 G (220MMOL) of 98percent acetic anhydride and 0. 42g (2MMOL) of monohydrated paratoluensulfonic acid are heated to 40°C, 14 G (140MOL) of hydrogen peroxide are then slowly added. Once the hydrogen peroxide is completed the mixture is heated to the reflux temperature, afterwards it is cooled and the phases are separated. The aqueous phase was treated with 50 ml of dichloromethane and with 37percent hydrochloric acid up to a pH value of about 1. The organic phase was washed twice with water and dried on anhydrous sodium sulphate. After filtration the organic phase is evaporated under vacuum at 30°C/24MBAR, thereby obtaining 4. 4g of a product which after crystallisation form CYCLOHEXANE/DICHLOROMETHANE has m. p. =6365°C whose NMR and MS correspond to those of the desired product. Stage #1: in dichloromethane

T=40°C; 10 h; Heating / reflux; Stage #2: With hydrogenchloride in dichloromethane; water

pH=1; Heating / reflux; Hide Experimental Procedure

ENDURA S.P.A.

Patent: WO2004/92106 A2, 2004 ; Location in patent: Page 14 ; Title/Abstract Full Text Show Details

14:EXAMPLE 14. Synthesis of 3,4-methylenedioxo-phenol

A mixture of 17, 7G (100MOL) of 1- (1, 3-BENZODIOXOL-5-YI)-L-PROPANONE and 30 ml of DICHLOROMETHANE are heated to 40°C ; then a solution of 40, Og (122MMOL) of phtalimido-peroxy hexanoic acid (P. A. P. from Solvay) (title 84.7percent w/w) in 100 ml of dichloromethaneare added slowly. Once the addition is completed the mixture is heated to reflux for 10 hours. Then it is cooled and treated as described in example 11 with suitable amounts of reactants. 6.4 G of a product are obtained which after crystallisation from cyclohexane/dichloromethane has m. p. 64-65°C and whose NMR and MS analyses correspond to those of the desired products.

Stage #1: With phthalic anhydride; toluene-4-sulfonic acid in dichloromethane

T=40°C; Stage #2: With dihydrogen peroxide in dichloromethane; water

Heating / reflux; Stage #3: With hydrogenchloride in dichloromethane; water

pH=1; Hide Experimental Procedure

ENDURA S.P.A.

Patent: WO2004/92106 A2, 2004 ; Location in patent: Page 13 ; Title/Abstract Full Text Show Details

12:EXAMPLE 12. Synthesis of 3,4-methylenedioxo-phenol

A mixture of 17. 7G (100MMOI) of 1-(1,3-benzodioxol-5-yl)-1-propanone, 50 ml of DICHLOROMETHANE, 33. OG (220MOL) of 97percent phthalic anhydride and 0. 42g (2MMOL) of monohydrated P-TOLUENSULFONIC acid are heated to 40°C, then 14. Og (140MMOL) of 35percent hydrogen peroxide. Once said addition is completed the reaction mixture is heated under reflux for 6 hours. The reaction mixture is cooled and unreacted phthalic anhydride is filtered and the organic solution obtained is treated as reported in Example 11, utilising the same amounts of reactants. 4.3g of a product are obtained which, after crystallisation of CYCLOHEXANE/DICHLOROMETHANE, has m. p =63-65°C, whose NMR and MS analyses correspond to those of the desired compound. Stage #1: With maleic anhydride; toluene-4-sulfonic acid in dichloromethane

T=40°C; Stage #2: With dihydrogen peroxide in dichloromethane; water

Heating / reflux; Stage #3: With hydrogenchloride in dichloromethane; water

pH=1; Hide Experimental Procedure

ENDURA S.P.A.

Patent: WO2004/92106 A2, 2004 ; Location in patent: Page 13-14 ; Title/Abstract Full Text Show Details

13:EXAMPLE 13. Synthesis of 3,4-methylenedioxo-phenol

A mixture of 17. 7g (100MOL) of 1- (1, 3-BENZODIOXOL-5-YL)-1-PROPANONE, 50 ml of dichloromethane, 21. 4G (218 MMOL) of maleic anhydride and 0. 42g (2MMOL) of monohydrated P-TOLUENSULFONIC acid are heated to 40°C, then 14. Og (140MOL) of 35percent hydrogen peroxide are slowly added. Once the addition is completed the mixture is heated under reflux for 6 hours, afterwards it is cooled and treated as described in example 11 with the same amounts of reactants. 6. 3g of a products are obtained which after crystallisation from cyclohexane/dichloromethane has a m. p. =63-65°C, whose NMR and MS analyses correspond to those of the desired product.

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Rx-ID: 5428742 Find similar reactions

Crosby,D.G.; Berthold,R.V.

Journal of Organic Chemistry, 1962 , vol. 27, p. 3083 - 3085 Full Text View citing articles Show Details

Minamikawa; Brossi

Tetrahedron Letters, 1978 , p. 3085 Full Text View citing articles Show Details

Ohno et al.

Bulletin of the Institute for Chemical Research, Kyoto University, 1960 , vol. 38, p. 34,38 Chem.Abstr., 1961 , # 22275d Full Text Show Details

Orphanos; Taurius

Canadian Journal of Chemistry, 1966 , vol. 44, p. 1875,1877 Full Text Show Details

ENDURA S.P.A.

Patent: WO2004/92106 A2, 2004 ; Location in patent: Page 11 ; Title/Abstract Full Text Show Details

Hide Experimental Procedure

Merck Patent Gesellschaft mit Beschrankter Haftung

Patent: US5821256 A1, 1998 ; Title/Abstract Full Text Show Details

...he customary manner and 2-(1,3-benzodioxol-5-yl)-2-(1,3-dihydro-1,3-dioxoisoindol-5-yloxy)-N-(4-tert-butylphenylsulfonyl)acetamide, m.p. 215°, is obtained; potassium salt of the compound FAB 575, m.p. 171°. Analogously, by reaction of methyl benzo[1,3]dioxol-5-ylbromoacetate with ... 5-hydroxybenzofuran 4-hydroxy-2-methylindole 5-hydroxy-1,3-benzodioxol,

Synthesize Find similar With triethylamine in various solvent(s) T=20°C; Kinetics; Further Variations:Reagents;

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Rx-ID: 9687716 Find similar reactions

Joshi; Naumov; Kapoor; Mukherjee; Hermann; Brede

Journal of Physical Organic Chemistry, 2004 , vol. 17, # 8 p. 665 - 674 Title/Abstract Full Text View citing articles Show Details

Synthesize Find similar With dihydrogen peroxide; titanium-silicalite catalyst (TS-1) in isobutyl methylketone; acetone

T=60°C; 5 h; Conversion of starting material; Hide Experimental Procedure

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Rx-ID: 23141818 Find similar reactions

BORREGAARD ITALIA S.P.A.

Patent: WO2004/14827 A1, 2004 ; Location in patent: Page 7-8 ; Title/Abstract Full Text Show Details

1:EXAMPLE 1

30 g of TS-1 catalyst, 150 g of methylisobutylketone, 150 g of acetone and 150 g (1.23 moles) of MDB, are charged into a reactor equipped with a stirrer, thermometer, condenser and heating/cooling jacket. The resulting suspension is heated to [60°C,] maintaining the mass under stirring. 84 g of H202 at [10percent] (0.25 moles) are then fed in about 4 hours, the temperature of the suspension being maintained at [60°C.] The suspension is left under stirring at [60°C] for an hour and the organic phase is subsequently analyzed after separation from the TS-1 catalyst. The following results are obtained from GLC analysis of the organic phase: MDB conversion = 15percent ; selectivity to 5-hydroxy-MDB = 62percent. With dihydrogen peroxide; titanium-silicalite catalyst (TS-1) in hexane; isobutyl methylketone

T=60°C; 5 h; Conversion of starting material; Hide Experimental Procedure

BORREGAARD ITALIA S.P.A.

Patent: WO2004/14827 A1, 2004 ; Location in patent: Page 9 ; Title/Abstract Full Text Show Details

4:EXAMPLE 4

The same procedure is used as in Example 1, except that 33 g of n-hexane are charged instead of acetone. The following results are obtained from GLC analysis of the organic phase: MDB conversion = 10percent; selectivity to [5-HYDROXY-MDB] = 70percent. With dihydrogen peroxide; titanium-silicalite catalyst (TS-1) in carbonic acid dimethyl ester

T=60°C; 5 h; Conversion of starting material; Hide Experimental Procedure

BORREGAARD ITALIA S.P.A.

Patent: WO2004/14827 A1, 2004 ; Location in patent: Page 9 ; Title/Abstract Full Text Show Details

5:EXAMPLE 5

The same procedure is used as in Example 1, except that 150 g of dimethyl carbonate are charged instead of the acetone/methylisobutylketone mixture. The following results are obtained from GLC analysis of the organic phase: MDB conversion = 13percent ; selectivity to 5-hydroxy-MDB = 52percent.

With dihydrogen peroxide; titanium-silicalite catalyst (TS-1) in acetonitrile

T=60°C; 5 h; Conversion of starting material; Hide Experimental Procedure

BORREGAARD ITALIA S.P.A.

Patent: WO2004/14827 A1, 2004 ; Location in patent: Page 9 ; Title/Abstract Full Text Show Details

6:EXAMPLE 6

The same procedure is used as in Example 1, except that 150 g of acetonitrile are charged instead of the acetone/methylisobutylketone mixture. The following results are obtained from GLC analysis of the organic phase: MDB conversion = 10percent; selectivity to 5-hydroxy-MDB = [45percent.] With dihydrogen peroxide; titanium-silicalite catalyst (TS-1) in tert-butyl alcohol

T=60°C; 5 h; Conversion of starting material; Hide Experimental Procedure

BORREGAARD ITALIA S.P.A.

Patent: WO2004/14827 A1, 2004 ; Location in patent: Page 9-10 ; Title/Abstract Full Text Show Details

7:EXAMPLE 7

The same procedure is used as in Example 1, except that 300 g of terbutanol are charged instead of the acetone/methylisobutylketone mixture. The following results are obtained from GLC analysis of the organic phase: MDB conversion = [15percent] ; selectivity to 5-hydroxy-MDB = 48percent. With dihydrogen peroxide; titanium-silicalite catalyst (TS-1) in acetone

T=60°C; 5 h; Conversion of starting material; Hide Experimental Procedure

BORREGAARD ITALIA S.P.A.

Patent: WO2004/14827 A1, 2004 ; Location in patent: Page 8 ; Title/Abstract Full Text Show Details

2:EXAMPLE 2

EXAMPLE 2 The same procedure is used as in Example 1 except that only 300 g of acetone are charged instead of the acetone/methylisobutylketone mixture. The following results are obtained from GLC analysis of the organic phase: MDB conversion = 12percent ; selectivity to [5-HYDROXY-MDB] = [58percent.]

With dihydrogen peroxide; titanium-silicalite catalyst (TS-1) T=60°C; 5 h; Conversion of starting material; Hide Experimental Procedure

BORREGAARD ITALIA S.P.A.

Patent: WO2004/14827 A1, 2004 ; Location in patent: Page 8 ; Title/Abstract Full Text Show Details

3:EXAMPLE 3

The same procedure is used as in Example 1, except that 70 g of H20 are charged instead of the mixture of sol- vents and 28 g of H202 at [30percent] (0.25 moles), are dosed. The following results are obtained from GLC analysis of the organic phase: MDB conversion = 10percent ; selectivity to 5-hydroxy-MDB = [25percent.]

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With hydrogenchloride in water

pH=8.5; Hide Experimental Procedure

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Rx-ID: 23164364 Find similar reactions

ENDURA S.P.A.

Patent: WO2004/92106 A2, 2004 ; Location in patent: Page 8-9 ; Title/Abstract Full Text Show Details

2A:Example 2A - Acid hydrolysis of sesamyl propanoate.

1200 ml of methanol and 3.4 G of 96percent sulphuric acid are added to the crude reaction product from example 1. The mixture is stirred at 40°C for 9 hours, then cooled and the solvent is evaporated under vacuum at 30°C/23 mbar. The remainder is re-dissolved in 500 ml of methylene chloride to which 790 mi of 2M sodium hydroxide are added. The mixture is then stirred for 10 minutes and the phases are separated. The aqueous phase is extracted with 50 mi of methylene chloride. The organic phase containing the ketone and the non-hydrolysed ester is recycled as described in the following example 3A. The aqueous phase containing the sodium sesamate is then added with 37percent HCI till to pH 8.5 to obtain sesamol in free form, which is then extracted with 50 mi of methylene chloride. The organic phase containing the sesamol is concentrated under vacuum at 30°C/23 mbar. The sesamol is distilled at 116°C/3-4 mbar; hydrolysis yield : 94.3percent.

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Stage #1: With sodium hydroxide; tetrabutyl-ammonium chloride; water in dichloromethane

T=20 - 25°C; 8 - 8.75 h; Stage #2: With hydrogenchloride in dichloromethane; water

pH=8.5; Hide Experimental Procedure

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Rx-ID: 23164366 Find similar reactions

ENDURA S.P.A.

Patent: WO2004/92106 A2, 2004 ; Location in patent: Page 9-10 ; Title/Abstract Full Text Show Details

2B; 3B; 4A:Example 2B Basic hydrolysis of sesamyl propanoate

EXAMPLE 4A-Basic hydrolysis 2.32 G (8 mmoles) of hydrated tetrabutylammonium chloride are added to the previous organic phase and 664 G (2.7 moles) of 4M NAOH are added over 45 minutes while maintaining the temperature at 20-25°C. After stirring for 8 hours at room temperature the phases are separated. 100 ml of CH2CI2 are added to the aqueous phase which is added with 37percent HGI till to pH 8.5. The phases are separated. The organic phase containing the sesamol is concentrated under vacuum at 30°C/23 mbar. The SESAMOL is distilled AT 116°C/34 mbar to obtain 82 G of product. Yield with respect to converted product: 92.3percent. The distilled sesamol is crystallised in a 1/2 (V/V) mixture of toluene/cyclohexane. The solid obtained is filtered off and dried under vacuum at 40°C/23 MBAR. 79 G OF crystallised SESAMOL with A concentration of 99. 7percent w/w are obtained. 1325 ml of 4M sodium hydroxide and 3.6 G (13 MMOLES) of 98percent hydrated tetrabutylammonium chloride are added to the organic phase in methylene chloride obtained at the end of the reaction in example 1. After stirring for 8 hours at room temperature, the phases are separated. 200 ml of methylene chloride are added to the aqueous phase, which is added with 37percent HCI till to pH 8.5 to release the sesamol which passes into the organic phase. The organic phase is separated and the solvent is evaporated under vacuum at 30°C/23 mbar. The sesamol is distilled at 116°C/23 mbar; hydrolysis

yield: 95.8percent.EXAMPLE 3B-Recycling of the product derived from basic hydrolysis Following hydrolysis in an alkaline environment as described in example 2B, the organic solution containing the unreacted ketone and the non-hydrolyzed ester is made up to the same quantity of ketone indicated in example 1, and reacted as in example 1. The hydrolysis reaction is carried out by the same operative method given in example 3B and using the same molar ratio of SESAMYL propanoate/NaOH, with no further addition of catalyst. After distillation sesamol is obtained with a hydrolysis yield equal to 94percent. A

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Rx-ID: 22848061 Find similar reactions

B: 23 %Chromat.

With hydrogen peroxide in water

T=50°C; 2 h; Acidic conditions;

DAICEL CHEMICAL INDUSTRIES, Ltd.

Patent: EP1167365 A1, 2002 ; Location in patent: Page 5 ; Title/Abstract Full Text Show Details

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A: 79%

With ethanol; sodium hydroxide

T=82 - 96°C; 4.5 h; Reflux; elimination of ethyl formate;

DAICEL CHEMICAL INDUSTRIES, Ltd.

Patent: EP1167365 A1, 2002 ; Location in patent: Page 5 ; Title/Abstract Full Text Show Details

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Rx-ID: 8645133 Find similar reactions

91%

With carbon tetrabromide in methanol

ether cleavage; 5 h; Heating;

Yadav; Reddy, B. V. Subba

Chemistry Letters, 2000 , # 5 p. 566 - 567 Title/Abstract Full Text View citing articles Show Details

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Rx-ID: 4936120 Find similar reactions

95%

With magnesium in methanol

4 h; Ambient temperature;

Sridhar, Madabhushi; Kumar, B. Ashok; Narender

Tetrahedron Letters, 1998 , vol. 39, # 18 p. 2847 - 2850 Title/Abstract Full Text View citing articles Show Details

88%

With potassium fluoride on basic alumina

Substitution; 0.05 h; microwave irradiation;

Sabitha, Gowravaram; Abraham, Sunny; Reddy, B. V. Subba; Yadav

Synlett, 1999 , # 11 p. 1745 - 1746 Title/Abstract Full Text View citing articles Show Details

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Elimination; 1 h;

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Rx-ID: 5343039 Find similar reactions

Watanabe, Makoto; Nishiyama, Masakazu; Koie, Yasuyuki

Tetrahedron Letters, 1999 , vol. 40, # 50 p. 8837 - 8840 Title/Abstract Full Text View citing articles Show Details

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Rx-ID: 17371122 Find similar reactions

Saito, Naoki; Tashiro, Kyoichi; Maru, Yukie; Yamaguchi, Kentaro; Kubo, Akinori

1: m-CPBA / CH2Cl2 / 4 h / Heating 2: 10percent aq. KOH / methanol / 2.5 h / Ambient temperature View Scheme

Journal of the Chemical Society, Perkin Transactions 1: Organic and Bio-Organic Chemistry (1972-1999), 1997 , # 1 p. 53 - 70 Title/Abstract Full Text Show Details

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Multi-step reaction with 2 steps 1: 30percent aq. H2O2 / 2-NO2C6H4SeSeC6H4NO2-2 / CH2Cl2 / 45 h / Ambient temperature 2: KOH / methanol / 1 h / Ambient temperature View Scheme

Rx-ID: 20379904 Find similar reactions

Syper, Ludwik

Synthesis, 1989 , # 3 p. 167 - 172 Title/Abstract Full Text Show Details

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T=180°C; 2 h; variation of time, temperature; sesamol enhances antioxidativ action of γ-tocopherol; Product distribution;

Rx-ID: 2301641 Find similar reactions

Fukuda, Yasuko; Nagata, Masayasu; Osawa, Toshihiko; Namiki, Mitsuo

Agricultural and Biological Chemistry, 1986 , vol. 50, p. 857 - 862 Title/Abstract Full Text Show Details

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A: 67% B: 8%

With dihydrogen peroxide; sulfuric acid in methanol

24 h; Ambient temperature;

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Matsumoto, Masakatsu; Kobayashi, Hisako; Hotta, Yasushi

Journal of Organic Chemistry, 1984 , vol. 49, # 24 p. 4740 - 4741

Title/Abstract Full Text View citing articles Show Details

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A: 67% B: 8%

With dihydrogen peroxide; sulfuric acid in methanol

24 h; Ambient temperature;

Matsumoto, Masakatsu; Kobayashi, Hisako; Hotta, Yasushi

Journal of Organic Chemistry, 1984 , vol. 49, # 24 p. 4740 - 4741 Title/Abstract Full Text View citing articles Show Details

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94%

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With 2-chloro-1,3,2-dithioborolane in dichloromethane

T=-78°C; 0.75 h;

Rx-ID: 2562618 Find similar reactions

Williams, D.R.; Sakdarat, Santi

Tetrahedron Letters, 1983 , vol. 24, # 37 p. 3965 - 3968 Title/Abstract Full Text View citing articles Show Details

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With mineral acids

Rx-ID: 5428743 Find similar reactions

Adriani

Z. Nahr.-Genussm., vol. 56, p. 187 Chem. Zentralbl., 1929 , vol. 100, # I p. 1012 Full Text Show Details

Malagnini; Armanni

Chemiker-Zeitung, Chemische Apparatur, 1907 , vol. 5, p. 884,133

Full Text View citing articles Show Details

Kreis

Chemiker-Zeitung, Chemische Apparatur, 1903 , vol. 27, p. 1030 Chemiker-Zeitung, Chemische Apparatur, 1904 , vol. 28, p. 957 Full Text View citing articles Show Details

With hydrogenchloride

Adriani

Z. Nahr.-Genussm., vol. 56, p. 187 Chem. Zentralbl., 1929 , vol. 100, # I p. 1012 Full Text Show Details Malagnini; Armanni Chemiker-Zeitung, Chemische Apparatur, 1907 , vol. 5, p. 884,133 Full Text View citing articles Show Details Kreis Chemiker-Zeitung, Chemische Apparatur, 1903 , vol. 27, p. 1030 Chemiker-Zeitung, Chemische Apparatur, 1904 , vol. 28, p. 957 Full Text View citing articles Show Details

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Rx-ID: 628646 Find similar reactions

Malagnini; Armanni

Rendiconti della Soc. chim. di Roma, 1907 , vol. 5, p. 135 Full Text Show Details